In this study, we utilize silver vanadium phosphorous oxide, Ag 2VO 2PO 4, as a model system to systematically study the impact of the constituents of a composite electrode, including polymeric and conductive additives, on electrochemistry. Notably, although highly resistive, this bimetallic cathode can be discharged as a pure electroactive material in the absence of a conductive additive as it generates an in situ conductive matrix via a reduction displacement reaction resulting in the formation of silver metal nanoparticles. Also, three different electrode compositions were investigated: Ag 2VO 2PO 4 only, Ag 2VO 2PO 44 with binder, and Ag 2VO 2PO 4 with binder and carbon. Constant current discharge, pulse testing and impedance spectroscopy measurements were used to characterize the electrochemical properties of the electrodes as a function of depth of discharge. In situ EDXRD was used to spatially resolve the discharge progression within the cathode by following the formation of Ag 0. Ex situ XRD and EXAFS modeling were used to quantify the amount of Ag 0 formed. Results indicate that the metal center reduced (V 5+ or Ag +) was highly dependent on composite composition (presence of PTFE, carbon), depth of discharge (Ag 0 nanoparticle formation), and spatialmore » location within the cathode. The addition of a binder was found to increase cell polarization, and the percolation network provided by the carbon in the presence of PTFE was further increased with reduction and formation of Ag 0. Lastly, this study provides insight into the factors controlling the electrochemistry of resistive active materials in composite electrodes.« less

@article{osti_1347289,
title = {Li/Ag2VO2PO4 batteries: the roles of composite electrode constituents on electrochemistry},
author = {Bock, David C. and Bruck, Andrea M. and Pelliccione, Christopher J. and Zhang, Yiman and Takeuchi, Kenneth J. and Marschilok, Amy C. and Takeuchi, Esther S.},
abstractNote = {In this study, we utilize silver vanadium phosphorous oxide, Ag2VO2PO4, as a model system to systematically study the impact of the constituents of a composite electrode, including polymeric and conductive additives, on electrochemistry. Notably, although highly resistive, this bimetallic cathode can be discharged as a pure electroactive material in the absence of a conductive additive as it generates an in situ conductive matrix via a reduction displacement reaction resulting in the formation of silver metal nanoparticles. Also, three different electrode compositions were investigated: Ag2VO2PO4 only, Ag2VO2PO44 with binder, and Ag2VO2PO4 with binder and carbon. Constant current discharge, pulse testing and impedance spectroscopy measurements were used to characterize the electrochemical properties of the electrodes as a function of depth of discharge. In situ EDXRD was used to spatially resolve the discharge progression within the cathode by following the formation of Ag0. Ex situ XRD and EXAFS modeling were used to quantify the amount of Ag0 formed. Results indicate that the metal center reduced (V5+ or Ag+) was highly dependent on composite composition (presence of PTFE, carbon), depth of discharge (Ag0 nanoparticle formation), and spatial location within the cathode. The addition of a binder was found to increase cell polarization, and the percolation network provided by the carbon in the presence of PTFE was further increased with reduction and formation of Ag0. Lastly, this study provides insight into the factors controlling the electrochemistry of resistive active materials in composite electrodes.},
doi = {10.1039/C6RA24024K},
journal = {RSC Advances},
number = 108,
volume = 6,
place = {United States},
year = {2016},
month = {11}
}

Silver vanadium phosphorous oxide, Ag 2V 2OPO 4, was used as a model system to systematically study the impact on the constituents of a composite electrode, including polymeric and conductive additives, on electrochemistry. Three different electrode compositions were investigated.

We study silver vanadium phosphorus oxide, Ag 2VO 2PO 4, that is a promising cathode material for Li batteries due in part to its large capacity and high current capability. Herein, a new synthesis of Ag 2VO 2PO 4 based on microwave heating is presented, where the reaction time is reduced by approximately 100× relative to other reported methods, and the crystallite size is controlled via synthesis temperature, showing a linear correlation of crystallite size with temperature. Notably, under galvanostatic reduction, the Ag 2VO 2PO 4 sample with the smallest crystallite size delivers the highest capacity and shows the highestmore » loaded voltage. Further, pulse discharge tests show a significant resistance decrease during the initial discharge coincident with the formation of Ag metal. Thus, the magnitude of the resistance decrease observed during pulse tests depends on the Ag 2VO 2PO 4 crystallite size, with the largest resistance decrease observed for the smallest crystallite size. Additional electrochemical measurements indicate a quasi-reversible redox reaction involving Li + insertion/deinsertion, with capacity fade due to structural changes associated with the discharge/charge process. In summary, this work demonstrates a faster synthetic approach for bimetallic polyanionic materials which also provides the opportunity for tuning of electrochemical properties through control of material physical properties such as crystallite size.« less

In this report, we describe the electrochemistry of hybrid dual silver vanadium phosphorus oxide/carbon fluoride (Ag 2VO 2PO 4/CF x) cathodes with various weight ratios. Through modification of the Ag 2VO 2PO 4/CF x ratio, we can control the gravimetric and volumetric capacity, as well as mitigate the voltage drop during high current pulses. The increase in impedance caused by irreversible LiF formation in CFx was reduced by the silver reduction-displacement during electrochemical discharge of the Ag 2VO 2PO 4. Moreover, the addition of graphite was shown to reduce initial voltage delay. When Ag 2VO 2PO 4 dominates the electrodemore » mass (i.e. 75/25 Ag 2VO 2PO 4/CF x) in the hybrid cathode, pulse testing shows less voltage drop and delay, but at the expense of capacity and energy density. As the amount of CFx in the composite increases (i.e. Ag 2VO 2PO 4/CF x ratio of to 50/50 or 25/75), charge capacity and energy density increases, but at the expense of larger voltage drops and delays early in the discharge process. Thus, controlling the Ag 2VO 2PO 4/CF x ratio can be used to tune the electrochemical properties of the dual cathode, allowing for optimization of capacity and power depending on the application.« less

In this study, the high capacity of primary lithium-ion cathode Ag 2VO 2PO 4 is facilitated by both displacement and insertion reaction mechanisms. Whether the Ag extrusion (specifically, Ag reduction with Ag metal displaced from the host crystal) and V reduction are sequential or concurrent remains unclear. A microscopic description of the reaction mechanism is required for developing design rules for new multimechanism cathodes, combining both displacement and insertion reactions. However, the amorphization of Ag 2VO 2PO 4 during lithiation makes the investigation of the electrode reaction mechanism difficult with conventional characterization tools. For addressing this issue, a combination ofmore » local probes of pair-distribution function and X-ray spectroscopy were used to obtain a description of the discharge reaction. We determine that the initial reaction is dominated by silver extrusion with vanadium playing a supporting role. In addition, once sufficient Ag has been displaced, the residual Ag + in the host can no longer stabilize the host structure and V–O environment (i.e., onset of amorphization). After amorphization, silver extrusion continues but the vanadium reduction dominates the reaction. As a result, the crossover from primarily silver reduction displacement to vanadium reduction is facilitated by the amorphization that makes vanadium reduction increasingly more favorable.« less